CN114988991A - Method for preparing isomeric aldehyde by olefin hydroformylation - Google Patents

Method for preparing isomeric aldehyde by olefin hydroformylation Download PDF

Info

Publication number
CN114988991A
CN114988991A CN202210602904.6A CN202210602904A CN114988991A CN 114988991 A CN114988991 A CN 114988991A CN 202210602904 A CN202210602904 A CN 202210602904A CN 114988991 A CN114988991 A CN 114988991A
Authority
CN
China
Prior art keywords
hydroformylation
reaction
solution
phosphine ligand
room temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210602904.6A
Other languages
Chinese (zh)
Other versions
CN114988991B (en
Inventor
臧甲忠
李晨
王鹏飞
王本雷
蒋凌云
李继霞
郝婷婷
张硕
于海斌
刘洋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Original Assignee
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CNOOC Energy Technology and Services Ltd, CNOOC Tianjin Chemical Research and Design Institute Co Ltd filed Critical CNOOC Energy Technology and Services Ltd
Priority to CN202210602904.6A priority Critical patent/CN114988991B/en
Publication of CN114988991A publication Critical patent/CN114988991A/en
Application granted granted Critical
Publication of CN114988991B publication Critical patent/CN114988991B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2221—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing isomeric aldehyde by olefin hydroformylation, which comprises the steps of carrying out hydroformylation reaction on low-carbon olefin and synthesis gas under the action of a catalyst to generate a product containing aldehyde; the catalyst comprises a rhodium complex and a phosphine ligand. The invention provides a phosphine ligand with a novel molecular structure, which is matched with a rhodium complex in situ to form an isomeric aldehyde high-selectivity catalytic system, so that the problem of low isomeric aldehyde selectivity in the existing low-carbon olefin hydroformylation technology is effectively solved, and the method has the advantage of preparing isomeric aldehyde with high selectivity under the mild reaction condition.

Description

Method for preparing isomeric aldehyde by olefin hydroformylation
Technical Field
The invention belongs to the technical field of chemical raw material preparation, and particularly relates to a matching process for preparing isomeric aldehyde by hydroformylation of low-carbon olefin.
Background
Iso-aldehydes such as iso-butyraldehyde, iso-valeraldehyde, iso-hexanal and the like have important application in organic chemical industry, and can be used for producing high-value-added chemicals such as high-performance materials, essence, spices and the like. With the continuous expansion of the downstream market of isomeric aldehyde, the demand of isomeric aldehyde also increases year by year. However, the research of the disclosed technology mainly focuses on improving the selectivity of normal aldehyde, and the research on improving the selectivity of isomeric aldehyde is not much.
In the hydroformylation of lower olefins, the study on the hydroformylation of propylene is the most widely studied. The hydroformylation of propylene refers to the hydroformylation reaction of propylene and synthesis gas under the catalysis of transition metal complexes, the primary products are n-butyraldehyde and isobutyraldehyde, the aldehyde group is one of the most active groups, and can be hydrogenated into alcohol, oxidized into acid, aminated into amine, and subjected to a series of reactions such as disproportionation, condensation, acetalization and the like, so that a product network with the hydroformylation of propylene as a core and rich content is formed.
At present, a rhodium/triphenylphosphine complex is generally used as a catalyst in a propylene hydroformylation industrial device, the rhodium/triphenylphosphine complex has good stability and catalytic activity, a product is mainly a mixture of n-butyl aldehyde and iso-butyl aldehyde, the design value of the ratio of the n-butyl aldehyde to the iso-butyl aldehyde in the product is 8-12, the n-butyl aldehyde is mainly used as the product, and a small amount of iso-butyl aldehyde is produced as a byproduct. The n-butyraldehyde can be hydrogenated to produce butanol, or condensed and hydrogenated by itself to produce isooctyl alcohol. For isobutyraldehyde, the downstream market is developed slowly, the demand is low, and the added value of products is low. In recent years, with the gradual increase of national environmental protection requirements, the rapid development of the powder coating industry is driven, so that the requirements of products such as neopentyl glycol, dodecyl alcohol ester and the like are rapidly increased, and the demand of isobutyraldehyde as a key raw material of the products is greatly increased.
However, since the conventional isobutyraldehyde production is mainly a byproduct in an industrial propylene hydroformylation plant, the yield is only about 12%, which means that the isobutyraldehyde production capacity of a 10 ten thousand ton/a propylene hydroformylation plant is only 1.2 ten thousand ton/a. Due to the limited supply of isobutyraldehyde, the market price of isobutyraldehyde fluctuates greatly, and the development of the downstream neopentyl glycol and dodecyl alcohol ester industry is severely restricted.
At present, a lot of documents report about the regulation of the ratio of n-butyraldehyde to iso-butyraldehyde in an industrial device for propylene hydroformylation, on one hand, the regulation is mainly realized by changing a hydroformylation catalytic system, and on the other hand, the regulation is realized by changing the existing hydroformylation reaction process conditions.
Chinese patent CN201080062977.6 discloses a method for adjusting the ratio of normal isomeric aldehyde in hydroformylation process by changing the adding amount of mixed ligand, wherein the normal/iso ratio can be adjusted between 0.6-30 by controlling the adding amount of organic diphosphite ligand and organic monophosphite ligand added into the reaction system.
Chinese patent CN201080063170.4 discloses a method for adjusting the ratio of normal isomeric aldehydes by changing the partial pressure of synthesis gas in the hydroformylation process, increasing the partial pressure of synthesis gas in the first reaction zone to decrease the normal to iso ratio or decreasing the partial pressure of synthesis gas in the first reaction zone to increase the normal to iso ratio.
Chinese patent CN201410199317.2 discloses a method for controlling the normal-to-iso ratio in a mixed ligand hydroformylation process by controlling the olefin partial pressure, which is to decrease the normal-to-iso ratio by decreasing the olefin partial pressure in the first reaction zone or increase the olefin partial pressure in the first reaction zone to increase the normal-to-iso ratio.
Chinese patent CN201910547457.7 discloses a catalyst composition for reducing the normal isomerization ratio of an olefin hydroformylation product, wherein the catalyst active component is rhodium salt, the cocatalyst is triphenylphosphine, an auxiliary agent A is a phosphine-containing alkyl ligand, and an auxiliary agent B is a hetero-benzene containing an indole structure. The catalyst composition is used for olefin hydroformylation, can reduce the normal isomerization proportion in products, and improves the selectivity and stability of the catalyst under the working condition of low normal-to-iso ratio (less than 10).
However, in the prior art, the reduction of the iso-aldehyde normal-iso ratio through process adjustment, such as the adjustment of carbon monoxide partial pressure, the adjustment of olefin partial pressure and the like, has a certain effect on the improvement of the iso-aldehyde yield, but causes the problems of the reduction of the olefin conversion rate, the reduction of the iso-aldehyde yield and the reduction of the service life of the rhodium catalyst. The mixed ligand system has a good effect on regulating the product aldehyde normal-to-iso ratio, but the separation difficulty of the catalyst and the product is increased due to different chemical properties of various added ligands, and the regulation has serious hysteresis due to the influence of the original ligand in the system, so that the industrial application difficulty is high.
Disclosure of Invention
The invention aims to overcome the problem of low yield of isomeric aldehyde in the existing low-carbon olefin hydroformylation technology, and provides a method for preparing isomeric aldehyde with high selectivity under mild reaction conditions by adopting an isomeric aldehyde high-selectivity catalytic system.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a method for preparing isomeric aldehyde by hydroformylation of low-carbon olefin comprises the steps of performing hydroformylation reaction on the low-carbon olefin and synthesis gas under the action of a catalyst to generate a product containing aldehyde; the catalyst comprises a rhodium complex and a phosphine ligand, wherein the structure of the phosphine ligand is shown as a general formula L:
Figure BDA0003670645730000031
wherein R1-R8 are respectively and independently C1-C10 alkyl, C5-C12 cycloalkyl or methoxy.
Preferably, the phosphine ligand is one or more of L1, L2, L3, L4, L5, L6, L7 and L8, and the structural formula of L1-L8 is as follows:
Figure BDA0003670645730000032
Figure BDA0003670645730000041
in the above technical scheme of the invention, the main component of the synthesis gas is H 2 And CO, H 2 And CO in a volume content of 70-100%, preferably in the range of 90-100%, H 2 The volume ratio of/CO is 0.5-4.0, preferably 0.9-1.1.
In the above technical solution of the present invention, the rhodium complex is selected from Rh (acac) (CO) 2 、Rh(acac)(C 2 H 4 )、HRh(CO)(PPh 3 ) 3 And Rh (Rh), (acac) and (CO) (PPh) 3 ) One or more of; wherein acac represents acetylacetone.
Preferably, the molar ratio of rhodium to phosphine ligand in the catalyst is 1:1-1:80, and the dosage of the catalyst is 10-1000 × 10 -4 % based on the total mass of the reaction system.
More preferably, the molar ratio of rhodium to phosphine ligand in the catalyst is 1:4-1:20, and the dosage of the catalyst is 50-300 × 10 -4 % based on the total mass of the reaction system.
Preferably, the hydroformylation reaction temperature is 40-150 ℃, and the reaction pressure gauge pressure is 0.5-5 MPa.
Preferably, the preparation method of the phosphine ligand of the catalyst comprises the following steps:
Figure BDA0003670645730000042
(1) dissolving substituted diphenol and pyridine in trichloromethane, dropwise adding trichloromethane solution of di-tert-butyl dicarbonate into the ice water bath solution of the substituted diphenol, and heating to room temperature after dropwise adding is finished, and stirring for 8-12 hours. Removing the solvent under reduced pressure, and washing residues with n-hexane to obtain an intermediate A, wherein the molar ratio of the substituted diphenol to the pyridine is 1: 10-1: 3, and the molar ratio of the substituted diphenol to the di-tert-butyl dicarbonate is) 0.8-1.2;
Figure BDA0003670645730000043
(2) mixing the intermediate A and triethylamine, dissolving the mixture in dichloromethane, then dripping a dichloromethane solution of phosphorus trichloride into the intermediate solution, stirring the reaction solution at room temperature for 2-4 hours after the dripping is completed, heating and refluxing for 0.5-2 hours, cooling, filtering, evaporating the filtrate to dryness to obtain an intermediate B, wherein the molar ratio of the intermediate A to the triethylamine is 1: 6-1: 1, and the molar ratio of the intermediate A to the phosphorus trichloride is 1: 5-1: 1;
Figure BDA0003670645730000051
(3) dissolving the intermediate B in tetrahydrofuran, dropwise adding the tetrahydrofuran solution of substituted phenol and pyridine into the intermediate B solution at room temperature, and stirring for 4-8 hours at room temperature after dropwise adding; and filtering the reaction solution, evaporating the filtrate to remove the solvent, and washing with acetonitrile to obtain a ligand L4, wherein the molar ratio of the intermediate B to the substituted phenol is 1: 5-1: 2, and the molar ratio of the intermediate B to the pyridine is 1: 10-1: 3.
Preferably, the catalyst is used by in situ coordination of a rhodium complex and a phosphine ligand in a synthesis gas atmosphere.
Preferably, the lower olefins are selected from linear olefins of C3-C5; further preferred are propylene, 1-butene, 2-butene, 1-pentene, 2-pentene and mixtures of the above olefins.
Compared with the prior art, the invention has the following remarkable effects:
1. the method of the invention uses the monophosphite type ligand in the hydroformylation reaction of low carbon olefin, and has the advantages of high product yield and high isomeric aldehyde selectivity, wherein the isomeric aldehyde selectivity is more than 80 percent and can be as high as 97.1 percent at most.
2. The preparation method of the monophosphite type ligand provided by the invention is simple and is easy to realize large-scale production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
The preparation process of the phosphine ligand L1 is as follows:
Figure BDA0003670645730000061
3,3 ', 5,5 ' -tetramethyl-2, 2 ' -biphenol (0.5mol) and pyridine (2.0mol) are dissolved in trichloromethane, trichloromethane solution of di-tert-butyl dicarbonate (0.5mol) is dripped into an ice-water bath solution of substituted biphenol, and after the dripping is finished, the temperature is raised to room temperature and the stirring is carried out for 10 hours. The solvent was removed under reduced pressure and the residue was washed with n-hexane to give the target intermediate a 1.
Figure BDA0003670645730000062
Mixing the intermediate A1(0.3mol) and triethylamine (1.1mol), dissolving the mixture in dichloromethane, then dropping a dichloromethane solution of phosphorus trichloride (1.2mol) into the intermediate solution, stirring the reaction solution at room temperature for 3 hours after the dropping is completed, heating and refluxing for 1 hour, cooling, filtering, and evaporating the filtrate to dryness to obtain the target intermediate B1.
Figure BDA0003670645730000063
Intermediate B1(0.2mol) was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of 2, 4-dimethylphenol (0.41mol) and pyridine (0.6mol) was added dropwise to the intermediate B1 solution at room temperature, and after completion of the addition, the mixture was stirred at room temperature for 6 hours. And filtering the reaction solution, evaporating the filtrate to remove the solvent, and washing with acetonitrile to obtain the ligand L1.
Preparation of isobutyraldehyde by catalyzing propylene hydroformylation through rhodium compound and phosphine ligand
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), phosphine ligand L1(0.4mmol), toluene (40mL) and nitrogen were substituted three times, propylene (99.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 1.8MPa of synthesis gas (H) was charged 2 Volume ratio of/CO 1; h 2 The content of CO is more than or equal to 99.9 percent) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 1.
Method for preparing isovaleraldehyde by catalyzing hydroformylation of 1-butene through rhodium compound and phosphine ligand
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), ligand L1(0.4mmol), toluene (40mL) and nitrogen were substituted three times, 1-butene (98.5 wt%, 10.0g) was charged, the temperature in the kettle was controlled at 90 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 2.
Example 2
The preparation process of the phosphine ligand L2 is as follows:
Figure BDA0003670645730000071
3,3 ', 5,5 ' -tetraethyl-2, 2 ' -biphenol (0.5mol) and pyridine (2.0mol) were dissolved in chloroform, a chloroform solution of di-tert-butyl dicarbonate (0.5mol) was added dropwise to an ice-water bath solution of a substituted biphenol, and after the addition was completed, the mixture was heated to room temperature and stirred for 10 hours. The solvent was removed under reduced pressure and the residue was washed with n-hexane to give the target intermediate a 2.
Figure BDA0003670645730000072
Mixing the intermediate A2(0.3mol) and triethylamine (1.1mol), dissolving the mixture in dichloromethane, then dripping a dichloromethane solution of phosphorus trichloride (1.2mol) into the intermediate solution, stirring the reaction solution at room temperature for 3 hours after the dripping is finished, then heating and refluxing for 1 hour, cooling and filtering, and evaporating the filtrate to dryness to obtain a target intermediate B2.
Figure BDA0003670645730000081
Intermediate B2(0.2mol) was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of 2, 4-diethylphenol (0.41mol) and pyridine (0.6mol) was added dropwise to the intermediate B2 solution at room temperature, and after completion of the addition, the mixture was stirred at room temperature for 6 hours. And filtering the reaction solution, evaporating the filtrate to remove the solvent, and washing with acetonitrile to obtain the ligand L2.
The procedure for the hydroformylation of propylene to produce isobutyraldehyde is the same as in the examples, except that: the phosphine ligand employed was ligand L2.
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), phosphine ligand L2(0.8mmol), toluene (40mL) and nitrogen were substituted three times, propylene (99.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 1.8MPa of synthesis gas (H) was charged 2 Volume ratio of/CO 1; h 2 The content of CO is more than or equal to 99.9 percent) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 1.
Method for preparing isovaleraldehyde by catalyzing 1-butene hydroformylation through rhodium compound and phosphine ligand
A100 mL autoclave was charged with Rh (acac) and (CO) 2 (0.04mmol), ligand L2(0.8mmol), toluene (40mL) and nitrogen were substituted three times, 1-butene (98.5 wt%, 10.0g) was charged, the temperature in the kettle was controlled to 90 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction liquid was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 2.
Example 3
The preparation process of the phosphine ligand L3 is as follows:
Figure BDA0003670645730000091
3,3 ', 5,5 ' -tetraisopropyl-2, 2 ' -biphenol (0.5mol) and pyridine (2.0mol) are dissolved in chloroform, a chloroform solution of di-tert-butyl dicarbonate (0.5mol) is added dropwise to an ice-water bath solution of substituted biphenol, and after the dropwise addition is finished, the temperature is raised to room temperature and the mixture is stirred for 10 hours. The solvent was removed under reduced pressure and the residue was washed with n-hexane to give the target intermediate a 3.
Figure BDA0003670645730000092
Mixing the intermediate A3(0.3mol) and triethylamine (1.1mol), dissolving the mixture in dichloromethane, then dripping a dichloromethane solution of phosphorus trichloride (1.2mol) into the intermediate solution, stirring the reaction solution at room temperature for 3 hours after the dripping is finished, then heating and refluxing for 1 hour, cooling and filtering, and evaporating the filtrate to dryness to obtain a target intermediate B3.
Figure BDA0003670645730000093
Intermediate B3(0.2mol) was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of 2, 4-diisopropylphenol (0.41mol) and pyridine (0.6mol) was added dropwise to the intermediate B3 solution at room temperature, and after completion of the addition, the mixture was stirred at room temperature for 6 hours. And filtering the reaction solution, evaporating the filtrate to remove the solvent, and washing with acetonitrile to obtain the ligand L3.
The procedure for the hydroformylation of propylene to produce isobutyraldehyde is the same as in the examples, except that: the phosphine ligand employed was ligand L3.
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), phosphine ligand L3(0.4mmol), toluene (40mL) and nitrogen were substituted three times, propylene (99.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 2MPa of synthesis gas (H) was charged 2 Volume ratio of/CO 1; h 2 The content of CO is more than or equal to 99.9 percent) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 1.
Method for preparing isovaleraldehyde by catalyzing hydroformylation of 1-butene through rhodium compound and phosphine ligand
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), ligand L3(0.4mmol), toluene (40mL) and nitrogen were substituted three times, 1-butene (98.5 wt%, 10.0g) was charged, the temperature in the kettle was controlled at 90 ℃ by a heating block, and then 1.8MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 2.
Example 4
The preparation process of the phosphine ligand L4 of the invention is as follows:
Figure BDA0003670645730000101
3,3 ', 5,5 ' -tetra-tert-butyl-2, 2 ' -biphenol (0.5mol) and pyridine (2.0mol) are dissolved in trichloromethane, trichloromethane solution of di-tert-butyl dicarbonate (0.5mol) is dripped into an ice-water bath solution of substituted biphenol, and after the dripping is finished, the temperature is raised to room temperature and the mixture is stirred for 10 hours. The solvent was removed under reduced pressure and the residue was washed with n-hexane to give the target intermediate a 4.
Figure BDA0003670645730000102
Mixing the intermediate A4(0.3mol) and triethylamine (1.1mol), dissolving the mixture in dichloromethane, then dripping a dichloromethane solution of phosphorus trichloride (1.2mol) into the intermediate solution, stirring the reaction solution at room temperature for 3 hours after the dripping is finished, then heating and refluxing for 1 hour, cooling and filtering, and evaporating the filtrate to dryness to obtain a target intermediate B4.
Figure BDA0003670645730000111
Intermediate B4(0.2mol) was dissolved in tetrahydrofuran, and a tetrahydrofuran solution of 2, 4-di-tert-butylphenol (0.41mol) and pyridine (0.6mol) was added dropwise to the intermediate B4 solution at room temperature, and after completion of the addition, the mixture was stirred at room temperature for 6 hours. And filtering the reaction solution, evaporating the filtrate to remove the solvent, and washing with acetonitrile to obtain the ligand L4.
The hydroformylation of propylene to produce isobutyraldehyde is the same as in example 1, except that: the phosphine ligand used was ligand L4.
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), phosphine ligand L4(0.4mmol), toluene (40mL) and nitrogen were substituted three times, propylene (99.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 1.8MPa of synthesis gas (H) was charged 2 Volume ratio of/CO 1; h 2 The content of CO is more than or equal to 99.9 percent) for hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 1.
Method for preparing isovaleraldehyde by catalyzing hydroformylation of 1-butene through rhodium compound and phosphine ligand
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), ligand L4(0.4mmol), toluene (40mL) and nitrogen were substituted three times, 1-butene (98.5 wt%, 10.0g) was charged, the temperature in the kettle was controlled to 90 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction liquid was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 2.
Example 5
Preparation of L4 referring to example 4, except for the hydroformylation reaction conditions in example 4, H2/CO purity 75.2% and the remaining 24.8% was N 2 Substitution of H 2 The results of the hydroformylation of propylene with a/CO content of 99.9% or more are shown in Table 1. The results of the 1-butene hydroformylation reaction are shown in Table 2.
Example 6
The preparation process of L4 is as shown in example 4, except that the hydroformylation reaction conditions in example 4 are increased to increase the catalyst charge
Process for preparing isobutyraldehyde by propylene hydroformylation
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.05mmol) of phosphineAfter the mixture of L4(0.5mmol) and toluene (40mL) was replaced with nitrogen three times, propylene (99.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 1.8MPa of synthesis gas (H) was introduced 2 Volume ratio of/CO 1; h 2 The content of CO is more than or equal to 99.9 percent) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 1.
Process for preparing isovaleraldehyde by hydroformylation of 1-butene
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.05mmol), ligand L4(0.5mmol), toluene (40mL) were purged with nitrogen three times, 1-butene (98.5 wt%, 10.0g) was introduced, the temperature in the kettle was controlled to 90 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was introduced 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 2.
Example 7
Preparation of L4 referring to example 4 except for the hydroformylation reaction conditions of example 4, the molar ratio of rhodium to phosphine ligand was reduced to 1:5
Process for preparing isobutyraldehyde by propylene hydroformylation
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), phosphine ligand L4(0.2mmol), toluene (40mL) and nitrogen were substituted three times, propylene (99.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 1.8MPa of synthesis gas (H) was charged 2 Volume ratio of/CO 1; h 2 The content of CO is more than or equal to 99.9 percent) to carry out hydroformylation reaction for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in table 1.
Process for preparing isovaleraldehyde by hydroformylation of 1-butene
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), ligand L4(0.2mmol), toluene (40mL) and nitrogen were substituted three times, 1-butene (98.5 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 85 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. Completion of the reactionAfter that, the reaction solution was cooled to room temperature, depressurized, and analyzed by gas chromatography, and the results are shown in Table 2.
Example 8
The process for the preparation of phosphine ligand L5 of the present invention is described in reference to example 4, except that 3,3 ', 5, 5' -tetra-tert-butyl-2, 2 '-biphenol as a starting material is replaced by 3, 3' -di-tert-butyl-5, 5 '-dimethoxy-2, 2' -biphenol, and other conditions are not changed.
Propylene hydroformylation for isobutyraldehyde and 1-butene hydroformylation for isovaleraldehyde according to example 1
Example 9
The procedure for the preparation of L6 of the phosphine ligand of the present invention is as described in example 4, except that 3,3 ', 5,5 ' -tetra-tert-butyl-2, 2 ' -biphenol as a starting material is replaced by 3,3 ' -di-tert-butyl-2, 2 ' -biphenol, and the others are unchanged.
Reaction conditions for the hydroformylation of propylene to produce isobutyraldehyde and 1-butene to produce isovaleraldehyde
Example 10
The procedure for the preparation of phosphine ligand L7 of the present invention is described in reference to example 4, except that 3,3 ', 5, 5' -tetra-tert-butyl-2, 2 '-biphenol as a raw material is replaced with 3, 3' -di-tert-butyl-5, 5 '-dimethoxy-2, 2' -biphenol, and 2, 4-di-tert-butylphenol as a raw material is replaced with 2-tert-butyl-4-methoxyphenol, and the others are unchanged.
Reaction conditions for the hydroformylation of propylene to produce isobutyraldehyde and 1-butene to produce isovaleraldehyde
Example 11
The procedure for the preparation of L8 of the phosphine ligand of the present invention is as described in example 4, except that 3,3 ', 5, 5' -tetra-tert-butyl-2, 2 '-biphenol as a raw material is replaced with 3, 3', 5,5 '-tetramethoxy-2, 2' -biphenol, and other conditions are not changed.
Propylene hydroformylation for isobutyraldehyde and 1-butene hydroformylation for isovaleraldehyde according to example 1
TABLE 1 results of the hydroformylation of propylene catalyzed by the ligands synthesized in examples 1 to 11
Figure BDA0003670645730000131
TABLE 2 results of the hydroformylation reaction of 1-butene catalyzed by the catalysts synthesized in examples 1 to 11
Figure BDA0003670645730000141
Example 12
Rh (acac) (CO) was charged into a 100mL autoclave 2 (0.04mmol), ligand L4(0.4mmol), toluene (40mL) and nitrogen were substituted three times, 1-pentene (97.0 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 90 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 5 hours. After the reaction, the reaction solution was cooled to room temperature, and the pressure was released, and the conversion of 1-pentene was 92.6%, the selectivity for pentane was 4.3%, and the selectivity for 2-methylpentanal was 91.3% by gas chromatography.
Example 13
A100 mL autoclave was charged with Rh (acac) and (CO) 2 (0.04mmol), ligand L5(0.4mmol), toluene (40mL) and nitrogen were substituted three times, 1-pentene (97.0 wt%, 10.0g) was charged, the temperature in the autoclave was controlled to 90 ℃ by a heating block, and then 1.6MPa of synthesis gas (H) was charged 2 The volume ratio of/CO is 1) to carry out hydroformylation reaction for 6 hours. After the reaction, the reaction solution was cooled to room temperature, and the pressure was released, and the conversion of 1-pentene was 97.8%, the selectivity for pentane was 2.7%, and the selectivity for 2-methylpentanal was 97.1% by gas chromatography.

Claims (10)

1. A method for preparing isomeric aldehyde by hydroformylation of low-carbon olefin is characterized in that the low-carbon olefin and synthesis gas are subjected to hydroformylation reaction under the action of a catalyst to generate a product containing isomeric aldehyde; the catalyst comprises a rhodium complex and a phosphine ligand, wherein the structure of the phosphine ligand is shown as a general formula L:
Figure FDA0003670645720000011
wherein R1-R8 are respectively and independently C1-C10 alkyl, C5-C12 cycloalkyl or methoxy; the low-carbon olefin is selected from linear olefins of C3-C5.
2. The method of claim 1, wherein the phosphine ligand is one or more of L1, L2, L3, L4, L5, L6, L7, and L8, and the structural formula of L1-L8 is as follows:
Figure FDA0003670645720000012
Figure FDA0003670645720000021
3. the method of claim 1, wherein the syngas has a major component of H 2 And CO, H 2 And CO in an amount of 70-100% by volume, H 2 The volume ratio of/CO is 0.5-4.0.
4. The method of claim 3, wherein the syngas H is 2 And CO in an amount of 90-100% by volume, H 2 The volume ratio of/CO is 0.9-1.1.
5. The process of claim 1, wherein the rhodium complex is selected from the group consisting of Rh (acac) (CO) 2 、Rh(acac)(C 2 H 4 )、HRh(CO)(PPh 3 ) 3 And Rh (acac) (PPh) 3 ) One or more of (a); wherein acac represents acetylacetone.
6. A process according to claim 1, wherein the molar ratio of rhodium to phosphine ligand in the catalyst is in the range 1:1 to 1:80, preferably 1:4 to 1: 20.
7. According to any one of claims 1-6The method is characterized in that the dosage of the catalyst is 10-1000 multiplied by 10 based on the total mass of the reaction system -4 % is preferably 50 to 300X 10 -4 ％。
8. The process according to any one of claims 1 to 6, wherein the hydroformylation reaction temperature is 40 to 150 ℃ and the reaction pressure gauge pressure is 0.5 to 5 MPa.
9. A process according to any one of claims 1 to 6, characterized in that the process for the preparation of the phosphine ligand of the catalyst comprises the steps of:
Figure FDA0003670645720000031
(1) dissolving substituted diphenol and pyridine in an organic solvent, dropwise adding di-tert-butyl dicarbonate dissolved in the organic solvent into an ice water bath solution of the substituted diphenol, heating to room temperature after dropwise adding is finished, stirring for 8-12 hours, removing the solvent under reduced pressure, and washing residues with a non-polar solvent to obtain an intermediate A, wherein the molar ratio of the substituted diphenol to the pyridine is 1: 10-1: 3, and the molar ratio of the substituted diphenol to the di-tert-butyl dicarbonate is 0.8-1.2;
Figure FDA0003670645720000032
(2) mixing an intermediate A (0.3mol) and triethylamine (1.1mol), dissolving the mixture in an organic solvent, then dropping an organic solvent of phosphorus trichloride (1.2mol) into the intermediate solution, stirring the reaction solution at room temperature for 2-4 hours after the dropping is finished, heating and refluxing for 0.5-2 hours, cooling, filtering, and evaporating the filtrate to dryness to obtain an intermediate B, wherein the molar ratio of the intermediate A to the triethylamine is 1: 6-1: 1, and the molar ratio of the intermediate A to the phosphorus trichloride is 1: 5-1: 1;
Figure FDA0003670645720000033
(3) dissolving the intermediate B (0.2mol) in an organic solvent, dropwise adding the organic solvent solution of substituted phenol and pyridine into the intermediate B solution at room temperature, and stirring for 4-8 hours at room temperature after dropwise adding; and filtering the reaction solution, evaporating the filtrate to remove the solvent, and washing to obtain a ligand L4, wherein the molar ratio of the intermediate B to the substituted phenol is 1: 5-1: 2, and the molar ratio of the intermediate B to the pyridine is 1: 10-1: 3.
10. The process of any one of claims 1 to 6, wherein the lower olefin is selected from the group consisting of propylene, 1-butene, 2-butene, 1-pentene, 2-pentene, and mixtures of the foregoing.
CN202210602904.6A 2022-05-31 2022-05-31 Method for preparing isomeric aldehyde by hydroformylation of olefin Active CN114988991B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210602904.6A CN114988991B (en) 2022-05-31 2022-05-31 Method for preparing isomeric aldehyde by hydroformylation of olefin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210602904.6A CN114988991B (en) 2022-05-31 2022-05-31 Method for preparing isomeric aldehyde by hydroformylation of olefin

Publications (2)

Publication Number Publication Date
CN114988991A true CN114988991A (en) 2022-09-02
CN114988991B CN114988991B (en) 2024-02-09

Family

ID=83030907

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210602904.6A Active CN114988991B (en) 2022-05-31 2022-05-31 Method for preparing isomeric aldehyde by hydroformylation of olefin

Country Status (1)

Country Link
CN (1) CN114988991B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0096987A2 (en) * 1982-06-11 1983-12-28 DAVY McKEE (LONDON) LIMITED Hydroformylation process
CN104058944A (en) * 2014-04-24 2014-09-24 上海华谊（集团）公司 Method for preparing aldehyde through alkene hydroformylation reaction
CN105085574A (en) * 2014-05-20 2015-11-25 赢创工业集团股份有限公司 Novel monophosphite ligands with a tertiary butyloxycarbonyl group
CN106083551A (en) * 2016-06-30 2016-11-09 成都欣华源科技有限责任公司 A kind of hydroformylation of propene prepares the method for butyraldehyde
CN106431869A (en) * 2016-10-09 2017-02-22 上海华谊（集团）公司 Method for producing aldehydes through olefin hydroformylation reaction
CN106588619A (en) * 2016-11-17 2017-04-26 万华化学集团股份有限公司 Method for preparing aldehyde through olefin hydroformylation
CN111348995A (en) * 2020-04-14 2020-06-30 万华化学集团股份有限公司 Method for preparing aldehyde by olefin hydroformylation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0096987A2 (en) * 1982-06-11 1983-12-28 DAVY McKEE (LONDON) LIMITED Hydroformylation process
CN104058944A (en) * 2014-04-24 2014-09-24 上海华谊（集团）公司 Method for preparing aldehyde through alkene hydroformylation reaction
CN105085574A (en) * 2014-05-20 2015-11-25 赢创工业集团股份有限公司 Novel monophosphite ligands with a tertiary butyloxycarbonyl group
CN106083551A (en) * 2016-06-30 2016-11-09 成都欣华源科技有限责任公司 A kind of hydroformylation of propene prepares the method for butyraldehyde
CN106431869A (en) * 2016-10-09 2017-02-22 上海华谊（集团）公司 Method for producing aldehydes through olefin hydroformylation reaction
CN106588619A (en) * 2016-11-17 2017-04-26 万华化学集团股份有限公司 Method for preparing aldehyde through olefin hydroformylation
CN111348995A (en) * 2020-04-14 2020-06-30 万华化学集团股份有限公司 Method for preparing aldehyde by olefin hydroformylation

Also Published As

Publication number Publication date
CN114988991B (en) 2024-02-09

Similar Documents

Publication Publication Date Title
CN108136381B (en) Hydroformylation catalyst, catalyst composition comprising the same, and method for preparing aldehyde using the same
CN113583045B (en) Catalyst composition containing bidentate phosphine ligand and application thereof
CN112898140B (en) Method for preparing aldehyde based on internal olefin catalyzed by phosphoramidite phosphine ligand
CN111348995A (en) Method for preparing aldehyde by olefin hydroformylation
CN112010906B (en) Bisphosphite and preparation method and application thereof
CN111686818B (en) Catalyst composition and application thereof in propylene hydroformylation reaction
CN114988991B (en) Method for preparing isomeric aldehyde by hydroformylation of olefin
CN107986943B (en) Synthesis method of cyclohexanedimethanol, catalyst and application thereof
CN110975941A (en) Hydroformylation reaction catalyst composition and method for preparing aldehyde through propylene hydroformylation reaction
CN114835751A (en) Phosphite ester-phosphate ester compound and preparation method and application thereof
CN113583046B (en) Bidentate phosphine ligand, preparation method and application thereof
CN113351249B (en) Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin
CN111320649B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN110372513B (en) Vinyl acetate hydroformylation method
CN114522735A (en) Solid catalyst for hydroformylation reaction of vinyl ester compound and preparation method thereof
CN108794527B (en) Bidentate phosphine ligand and application thereof in hydroformylation reaction
CN115594716B (en) Ligand for preparing branched aldehyde by catalyzing olefin hydroformylation reaction, preparation method and application thereof
CN115646552B (en) Catalyst for olefin hydroformylation and preparation method and application thereof
CN115701418B (en) Aldol composition and preparation method thereof, and method for continuously preparing aldehyde and alcohol
CN114832860A (en) Olefin hydroformylation catalyst composition and preparation method and application thereof
CN111320652B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method
CN117399073A (en) Hydrolysis-resistant catalyst for increasing yield of isobutyraldehyde through hydroformylation of propylene and application of catalyst
CN108586530B (en) Bidentate phosphine ligand and its application in hydroformylation reaction
CN113788857A (en) Phosphate ligand, preparation method and application thereof in preparation of linear aldehyde by catalyzing hydroformylation of terminal olefin
CN111320654B (en) Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant